CN106661140B - Manufacturing method, conjugated diolefin polymer, rubber composition and the tire of conjugated diolefin polymer - Google Patents
Manufacturing method, conjugated diolefin polymer, rubber composition and the tire of conjugated diolefin polymer Download PDFInfo
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- CN106661140B CN106661140B CN201580044464.5A CN201580044464A CN106661140B CN 106661140 B CN106661140 B CN 106661140B CN 201580044464 A CN201580044464 A CN 201580044464A CN 106661140 B CN106661140 B CN 106661140B
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- conjugated diolefin
- manufacturing
- diolefin polymer
- isoprene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 182
- 239000000203 mixture Substances 0.000 title claims abstract description 169
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 144
- 150000001993 dienes Chemical class 0.000 title claims abstract description 136
- 229920001971 elastomer Polymers 0.000 title claims description 34
- 239000005060 rubber Substances 0.000 title claims description 34
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 121
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- -1 rare-earth compound Chemical class 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 129
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 126
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 claims description 66
- 229920001400 block copolymer Polymers 0.000 claims description 49
- 229920005604 random copolymer Polymers 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 41
- 229910052782 aluminium Inorganic materials 0.000 claims description 38
- 239000004411 aluminium Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000002469 indenes Chemical class 0.000 claims description 11
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 150000002220 fluorenes Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 103
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 69
- 238000006243 chemical reaction Methods 0.000 description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000003197 catalytic effect Effects 0.000 description 30
- 230000008569 process Effects 0.000 description 27
- 229920002554 vinyl polymer Polymers 0.000 description 27
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- 230000000052 comparative effect Effects 0.000 description 24
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- 229910052688 Gadolinium Inorganic materials 0.000 description 22
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000006698 induction Effects 0.000 description 18
- 239000011572 manganese Substances 0.000 description 18
- BGLQFLIZWKWFBT-UHFFFAOYSA-N 3-benzyl-1h-indene Chemical class C=1CC2=CC=CC=C2C=1CC1=CC=CC=C1 BGLQFLIZWKWFBT-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 15
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- 238000009826 distribution Methods 0.000 description 13
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- 230000007613 environmental effect Effects 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 12
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000002879 Lewis base Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000007527 lewis bases Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 231100000331 toxic Toxicity 0.000 description 7
- 230000002588 toxic effect Effects 0.000 description 7
- PZZIWXQGJNDBRF-UHFFFAOYSA-N 2-phenyl-2,3-dihydro-1h-indene Chemical compound C1C2=CC=CC=C2CC1C1=CC=CC=C1 PZZIWXQGJNDBRF-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical class CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- LEYWWWZANZXECD-UHFFFAOYSA-N 1-methyl-2-phenyl-2,3-dihydro-1h-indene Chemical compound C1C2=CC=CC=C2C(C)C1C1=CC=CC=C1 LEYWWWZANZXECD-UHFFFAOYSA-N 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
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- 229910001507 metal halide Inorganic materials 0.000 description 3
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- NBHBNYRLTADHQY-UHFFFAOYSA-N 1-benzyl-1h-indene Chemical class C1=CC2=CC=CC=C2C1CC1=CC=CC=C1 NBHBNYRLTADHQY-UHFFFAOYSA-N 0.000 description 2
- RGOUNIRUASSINF-UHFFFAOYSA-N 1-benzyl-2-phenyl-2,3-dihydro-1h-indene Chemical compound C=1C=CC=CC=1CC(C1=CC=CC=C1C1)C1C1=CC=CC=C1 RGOUNIRUASSINF-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 2
- QAUQHTFRJMMRFK-UHFFFAOYSA-N 2-benzyl-1h-indene Chemical class C=1C2=CC=CC=C2CC=1CC1=CC=CC=C1 QAUQHTFRJMMRFK-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- RFONJRMUUALMBA-UHFFFAOYSA-N 2-methanidylpropane Chemical compound CC(C)[CH2-] RFONJRMUUALMBA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
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- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052773 Promethium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
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- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- OZNCPAQBJMPCIO-UHFFFAOYSA-N buta-1,3-diene;penta-1,3-diene Chemical compound C=CC=C.CC=CC=C OZNCPAQBJMPCIO-UHFFFAOYSA-N 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
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- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 2
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
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- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
- C08F4/545—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The purpose of the present invention is to provide a kind of manufacturing methods of the conjugated diolefin polymer of robustness that can be improved polymerization reaction system.It is a further object of the present invention to provide the conjugated diolefin polymers for being manufactured by the manufacturing method and being had high cis-1,4 chaining.A kind of manufacturing method of conjugated diolefin polymer, it is characterised in that carry out polymerized conjugated diene monomer using the polymerization catalyst composition for including rare-earth compound and the compound containing cyclopentadienyl skeleton；A kind of conjugated diolefin polymer, it is characterised in that manufactured by the manufacturing method and cis--Isosorbide-5-Nitrae linkage content is 95% or more.
Description
Technical field
This disclosure relates to the manufacturing method of conjugated diolefin polymer, conjugated diolefin polymer, rubber composition and tire.
Background technique
The rubber products such as tire require excellent damage-resistant (breaking resistance), abrasion resistence and
Resistance to crack growth resistance etc..As such, it is known to use the natural rubber with excellent resilience is as the raw material for being used for rubber product.In recent years
Come, since the price of the reduction of rubber tree resource, natural rubber has gone up.Therefore, have and the comparable characteristic of natural rubber
Synthetic rubber be necessary.
Natural rubber is substantially by having almost 100% cis--Isosorbide-5-Nitrae-linkage content polyisoprene to form, and people
Think that the molecular structure of the polymer produces elasticity.Knowledge based on these natural rubbers, to high-cis-Isosorbide-5-Nitrae-
The conjugated diolefin polymer of linkage content and the manufacturing method of such conjugated diolefin polymer is actively studied.
Use the catalyst formed by the metallocene cationoid complex of gadolinium compound is as the method for major catalyst
The manufacturing method of the known conjugated diolefin polymer with high-cis -1,4- linkage content is ((specially referring to JP 2004-027179 A
Sharp document 1)).In previous building methods, boron compound or aluminium alkoxide compound (especially PMMAO) etc. also serve as co-catalysis
Agent.
Reference listing
Patent document
Patent document 1:JP 2004-027179 A
Summary of the invention
Problems to be solved by the invention
However, in the manufacturing method of aforementioned known conjugated diolefin polymer, in order to dissolve polymerization catalyst group used
The compound of the major catalyst of object is closed, toxic and relatively expensive aromatic hydrocarbon (such as toluene) must be as the solvent of polymerization reaction.
It is thus known that the manufacturing method of conjugated diolefin polymer carry and cannot be substantially reduced the same of environmental pressure and manufacturing cost
When manufacture conjugated diolefin polymer risk.
Therefore it provides the conjugation two of conjugated diolefin polymer can be manufactured while reducing environmental pressure and manufacturing cost
The manufacturing method of alkene polymer will be beneficial.
There is provided it is being manufactured by the manufacturing method, with high cis-1,4-linkage content conjugated diolefin polymer also will be to have
Benefit.Further it is provided that the rubber composition including the conjugated diolefin polymer will be beneficial.It provides and uses the rubber composition
The tire of manufacture also will be beneficial.
The solution to the problem
The main idea of the disclosure is as follows.
The manufacturing method of the conjugated diolefin polymer of the disclosure include using include rare-earth compound and have be selected from
By at least one for the group that substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes and substituted or unsubstituted fluorenes form
The polymerization catalyst composition of the compound of cyclopentadienyl skeleton carrys out polymerized conjugated diene monomer.
According to the manufacturing method of the conjugated diolefin polymer of the disclosure, it is not necessary to be made using toxic and relatively expensive aromatic hydrocarbon
For the solvent of polymerization reaction.Therefore, according to the manufacturing method of the conjugated diolefin polymer of the disclosure, conjugated diolefin polymer can be with
It is manufactured while reducing environmental pressure and manufacturing cost.
In the manufacturing method of the conjugated diolefin polymer of the disclosure, rare-earth compound is preferably indicated by formula (1):
M-(AQ1)(AQ2)(AQ3) (1)
Wherein M indicates at least one element selected from the group being made of scandium, yttrium and lanthanide series；AQ1、AQ2And AQ3Respectively
For similar and different functional group；A indicates at least one selected from the group being made of nitrogen, oxygen and sulphur；With the rare earth element
Closing object includes at least one M-A key.
In the manufacturing method of the conjugated diolefin polymer of the disclosure, it is also preferable to include by formula for polymerization catalyst composition
(2) organo-metallic compound indicated:
YR1 aR2 bR3 c (2)
Wherein Y is the metallic element selected from the group being made of the 1st race of periodic table, the 2nd race, the 12nd race and the 13rd race；R1And R2
Respectively hydrogen atom or the alkyl with 1 to 10 carbon atom；R3For the alkyl with 1 to 10 carbon atom；R1、R2And R3That
This is identical or different；When Y is the metallic element of the 1st race, a is that 1 and b and c is 0；When the metal that Y is the 2nd race or the 12nd race
When element, a and b is 1 and c is 0；When Y is the metallic element of the 13rd race, a, b and c are 1.In addition, R1、R2And R3In extremely
It is one of few to be more preferably different.
In the manufacturing method of the conjugated diolefin polymer of the disclosure, the compound with the cyclopentadienyl skeleton is preferred
It is substituted or unsubstituted indenes.
In the manufacturing method of the conjugated diolefin polymer of the disclosure, it is also preferable to include aikyiaiurnirsoxan betas for polymerization catalyst composition
Compound, the aluminium alkoxide compound are more preferably MMAO or TMAO.
In the manufacturing method of the conjugated diolefin polymer of the disclosure, polymerization catalyst composition more preferably further includes halogen
Compound.Halogen compounds and the molar ratio of rare-earth compound are preferably 1.0 to 10.
In addition, in the manufacturing method of the conjugated diolefin polymer of the disclosure, polymerization catalyst composition it is preferably not included that
Aromatic hydrocarbon.
In addition, conjugate diene monomer is preferably isoprene in the manufacturing method of the conjugated diolefin polymer of the disclosure
With 1,3- butadiene.
The conjugated diolefin polymer of the disclosure by aforementioned conjugated diolefin polymer manufacturing method manufacture, and its cis- -1,
4- linkage content is 95% or more.
The conjugated diolefin polymer of the disclosure has high cis- -1,4- linkage content.It is, therefore, possible to provide having abundant
The conjugated diolefin polymer of elasticity.
The isoprene-butadiene block copolymer of the disclosure can be by manufacturer's legal system of aforementioned conjugated diolefin polymer
It makes.
The isoprene-butadiene random copolymer of the disclosure can be by manufacturer's legal system of aforementioned conjugated diolefin polymer
It makes.
The rubber composition of the disclosure includes aforementioned conjugated diolefin polymer.
The rubber composition of the disclosure can obtain the effect of the conjugated diolefin polymer of the disclosure.
The manufacture of the tire used of the disclosure rubber composition.
The tire of the disclosure can obtain the effect of the conjugated diolefin polymer of the disclosure.
The effect of invention
According to the manufacturing method of the conjugated diolefin polymer of the disclosure, conjugated diolefin polymer can reduce environmental pressure
It is manufactured while with manufacturing cost.Furthermore using the conjugated diolefin polymer of the disclosure, can provide with high cis- -1,
The conjugated diolefin polymer of 4- linkage content.In addition, the rubber composition of the disclosure can obtain the polymerization of conjugated dienes of the disclosure
The effect of object.Furthermore the tire of the disclosure can obtain the effect of the conjugated diolefin polymer of the disclosure.
Specific embodiment
The manufacturing method of the conjugated diolefin polymer of the disclosure, the polymerization of conjugated dienes of the disclosure is discussed in detail below
The embodiment of the tire of object, the rubber composition of the disclosure and the disclosure.
The manufacturing method of the conjugated diolefin polymer of the disclosure be use the disclosure an embodiment it is polymerization catalyzed
The method of agent composition polymerized conjugated diene monomer, the polymerization catalyst composition include rare-earth compound and have ring
The compound of cyclopentadiene skeleton.
According to the manufacturing method of the conjugated diolefin polymer of the disclosure, the preparation and conjugated diene of polymerization catalyst composition
The polymerization of monomer can carry out in one pot, to allow the process for omitting purified catalyst and obtain the effect for reducing manufacturing cost
Fruit and effective activation catalyst.
The manufacturing method of known conjugated diolefin polymer uses the metallocene cationoid complex shape by gadolinium compound
At catalyst as major catalyst.In order to dissolve the compound of major catalyst, toxic and relatively expensive aromatic hydrocarbon (such as first
Benzene) it must be as the solvent of polymerization reaction.It is thus known that the manufacturing method of conjugated diolefin polymer carry cannot be abundant
The risk of conjugated diolefin polymer is manufactured while reducing environmental pressure and manufacturing cost.
The manufacturing method of the conjugated diolefin polymer of the disclosure uses rare-earth compound as major catalyst and uses
Compound with cyclopentadienyl skeleton is as additive.Major catalyst and additive are soluble in except aromatic hydrocarbon (toluene etc.)
In solvent (such as hexane) in addition, and toxic and relatively expensive aromatic hydrocarbon is not absolutely essential as the molten of polymerization reaction
Agent.In other words, it is possible to reduce use toxic and relatively expensive aromatic hydrocarbon as the necessity of the solvent of polymerization reaction.Therefore,
According to the manufacturing method of the conjugated diolefin polymer of the present embodiment, conjugated diolefin polymer can reduce environmental pressure and system
Cause the manufacture of this while.
In the manufacturing method according to the conjugated diolefin polymer of the present embodiment, conjugation can be played in the reaction system
The compound with cyclopentadienyl skeleton of ligand effect is used as additive.Compound with cyclopentadienyl skeleton plays improvement
The effect of catalytic activity in reaction system.Therefore, foundation is gathered according to the manufacturing method of the conjugated diolefin polymer of the present embodiment
Reaction time needed for closing can be kept as it is relatively short, and the reaction temperature needed for polymerizeing can be set to it is relatively high so that poly-
The robustness (robustness) for closing reaction system increases.
(manufacturing method of conjugated diolefin polymer)
The example (example manufacturing process) of the manufacturing method of the conjugated diolefin polymer of the disclosure specifically includes:
Prepare the monomer preparatory process of conjugate diene monomer；
Polymerization catalyst composition of the preparation including rare-earth compound and the compound with cyclopentadienyl skeleton is (real
Example polymerization catalyst composition) catalyst system preparation section；With
By mixing conjugate diene monomer and polymerization catalyst composition come the polymerization reaction of polymerized conjugated diene monomer
Process.
Polymerization catalyst composition-
The polymerization catalyst composition of the disclosure of the example manufacturing process of conjugated diolefin polymer for the disclosure
Example (example polymerization catalyst composition) includes rare-earth compound and the compound with cyclopentadienyl skeleton.
The example polymerization catalyst composition of the disclosure is described below.
Example polymerization catalyst composition needs to include following compounds:
Rare-earth compound (component (A))；With
Compound (component (B)) with cyclopentadienyl skeleton.
Example polymerization catalyst composition may also include following compounds:
Organo-metallic compound (component (C))；
Aluminium alkoxide compound (component (D))；With
Halogen compounds (component (E)).
Example polymerization catalyst composition has highly dissoluble preferably in aliphatic hydrocarbon and is formed preferably in aliphatic hydrocarbon equal
Even solution.The example of aliphatic hydrocarbon includes hexane, hexamethylene and pentane.
Example polymerization catalyst composition is it is preferably not included that aromatic hydrocarbon.The example of aromatic hydrocarbon includes benzene, toluene and dimethylbenzene.
Statement " not including aromatic hydrocarbon " refer to include aromatic hydrocarbon in polymerization catalyst composition ratio less than 0.1 weight
Measure %.
-- rare-earth compound (component (A)) --
Component (A) can be compound (the rare earth containing rare earth element with metal-nitrogen key (M-N key)
Element containing compound) or this contain the compound of rare earth element and the reaction product of lewis base.
The example of compound containing rare earth element includes containing scandium, yttrium or the group of the lanthanides being made of the element of atomicity 57 to 71
The compound of element.Specifically, lanthanide series is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
The example of lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethyl-phosphine, lithium chloride, neutrality alkene
Hydro carbons and neutral alkadiene.
Containing the compound of rare earth element or this contain the compound of rare earth element and the reaction product of lewis base preferably dilute
Do not have key between earth elements and carbon.When the reaction product of the compound and lewis base containing rare earth element does not have rare earth member
When element-carbon key, reaction product is stable and is easily processed.
Can be used alone one kind of component (A), or two or more combinations can be used.
Component (A) is preferably the compound indicated by formula (1):
M-(AQ1)(AQ2)(AQ3) (1)
Wherein M indicates at least one element selected from the group being made of scandium, yttrium and lanthanide series；AQ1、AQ2And AQ3Respectively
For similar and different functional group；A indicates at least one selected from the group being made of nitrogen, oxygen and sulphur；And the rare earth element
Compound includes at least one M-A key.
Specifically, lanthanide series is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Using aforesaid compound, the catalytic activity in reaction system can be improved, the reaction time can be shortened, and can be mentioned
High reaction temperature.
The preferred gadolinium of M in formula (1) is to increase catalytic activity and reaction controllability.
When the A in formula (1) is nitrogen, then by AQ1、AQ2And AQ3(that is, NQ1、NQ2And NQ3) indicate functional group example
Including amide groups.In the case, which has 3 M-N keys.
The example of amide groups includes aliphatic amides base such as dimethyl acylamino, diethyl acylamino and diisopropylamide base
Deng；Aryl amido group such as phenyl acylamino, 2,6- di-tert-butyl-phenyl amide groups, 2,6- diisopropyl phenyl amide groups, 2,6-
Di neo-pentyl phenyl acylamino, 2- tert-butyl -6- isopropyl phenyl amide groups, 2- tert-butyl -6- neopentyl phenyl amide groups, 2-
Isopropyl -6- neopentyl phenyl amide groups and 2,4,6- tert-butyl-phenyl amide groups etc.；With double-trialkylsilyl amide base
Such as double-trimethylsilylamide base.Particularly, preferably double-three for the dissolubility for aliphatic hydrocarbon and aromatic hydrocarbon
Methyl silicane base amide groups.It can be used alone one kind of foregoing amides base, or two or more combinations can be used.
According to this structure, component (A) can be the compound containing 3 M-N keys.Therefore, each key becomes chemical equivalence, and
The structure of compound becomes stable, so that compound be made to be easily processed.
Furthermore previous constructions also improve the catalytic activity in reaction system.Therefore, the reaction time can further shorten,
And reaction temperature can be increased further.
When A is oxygen, the component (A) indicated by formula (1) can be any component, such as the rare earth alcohol indicated by following formula (1a)
Salt:
(RO)3M (1a)
Or the rare earth carboxylate indicated by following formula (1b):
(R-CO2)3M (1b)
Each R in formula (1a) and (1b) is the alkyl with 1 to 10 carbon atom, and can be identical or different.
As component (A), do not have the compound of key preferably between rare earth element and carbon.Therefore, above compound (1a)
Or compound (1b) can be properly used.
When A is sulphur, then the component (A) indicated by formula (1) can be any component, such as the rare earth indicated by following formula (1c)
Alkyl sulfide alkoxide:
(RS)3M (1c)
Or the compound indicated by following formula (1d):
(R-CS2)3M (1d)
Each R in formula (1c) and (1d) is the alkyl with 1 to 10 carbon atom, and can be identical or different.
As component (A), do not have the compound of key preferably between rare earth element and carbon.Therefore, above compound (1c)
Or compound (1d) can be properly used.
-- compound (component (B)) with cyclopentadienyl skeleton --
Component (B) can be any component with cyclopentadienyl skeleton, such as cyclopentadiene and all cyclopentadiene derive
Object.
In the present embodiment, especially for allowing advantageously to increase the volume as polymerization catalyst, shorten reaction
Time and raising reaction temperature, can be used to be selected from (is had by substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes
The compound of indenyl) and substituted or unsubstituted fluorenes composition at least one of group.
It can be used alone one kind of the compound with cyclopentadienyl skeleton, or two or more groups can be used
It closes.
The example of substituted cyclopentadiene includes pentamethylcyclopentadiene, tetramethyl-ring pentadiene, isopropylcyclopentadiene
With trimethyl silyl-tetramethyl-ring pentadiene etc..
The example of substituted indenes includes indenes, 2- phenyl -1H- indenes, 3- benzyl -1H- indenes, 3- methyl -2- phenyl -1H- indenes, 3-
Benzyl -2- phenyl -1H- indenes and 1- benzyl -1H- indenes etc..Particularly, in order to reduce molecular weight distribution, preferably 3- benzyl -1H- indenes
With 1- benzyl -1H- indenes.
The example of substituted fluorenes includes trimethyl silyl fluorenes and isopropyl fluorenes etc..
According to this structure, can increase including the conjugated electrons number in the compound with cyclopentadienyl skeleton, and can
To further increase the catalytic activity in reaction system.Therefore, the reaction time can further shorten, and reaction temperature can be with
Further increase.
-- organo-metallic compound (component (C)) --
Component (C) is the compound indicated by formula (2):
YR4 aR5 bR6 c (2)
Wherein Y is the metallic element selected from the group being made of the 1st race of periodic table, the 2nd race, the 12nd race and the 13rd race；R4And R5
Respectively hydrogen atom or the alkyl with 1 to 10 carbon atom；R6For the alkyl with 1 to 10 carbon atom；R4、R5And R6That
This is identical or different；When Y is the metallic element of the 1st race, a is that 1 and b and c is 0；When the metal that Y is the 2nd race or the 12nd race
When element, a and b is 1 and c is 0；When Y is the metallic element of the 13rd race, a, b and c are 1.
R in order to increase catalytic activity, in formula (2)4、R5And R6At least one of be preferably different.
More specifically, component (C) is preferably the organo-aluminum compound indicated by formula (3):
AlR7R8R9 (3)
Wherein R7And R8Respectively hydrogen atom or the alkyl with 1 to 10 carbon atom, R9For with 1 to 10 carbon atom
Alkyl, and R7、R8And R9It can be the same or different from each other.
The example of organo-aluminum compound includes: trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three positive fourths
Base aluminium, triisobutyl aluminium, tri-tert aluminium, three amyl aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum；Diethyl hydrogenation
Aluminium, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminium hydride, dihexyl aluminum hydride, two isohesyl aluminum hydrides,
Dioctyl aluminum hydride, diisooctyl aluminum hydride；Ethyl dihydroaluminium, n-propyl aluminum dihydride and isobutyl group aluminum dihydride, wherein
It is preferred that triethyl aluminum, triisobutyl aluminium, diethylaluminum hydride and diisobutyl aluminium hydride, particularly preferred diisobutyl aluminium hydride.
It can be used alone one kind of organo-aluminum compound, or two or more combinations can be used.
-- aluminium alkoxide compound (component (D)) --
Component (D) is the compound by contacting organo-aluminum compound and condensing agent.
By using component (D), the catalytic activity that can be further improved in polymerization reaction system.Therefore, the reaction time can
Further shorten, reaction temperature can be increased further.
The example of organo-aluminum compound includes trialkylaluminium such as trimethyl aluminium, triethyl aluminum and triisobutyl aluminium etc., and its
Mixture.In particular it is preferred to the mixture of trimethyl aluminium, trimethyl aluminium and tri-butyl aluminum.
The example of condensing agent includes water.
The example of component (D) includes the aikyiaiurnirsoxan beta indicated by formula (4):
-(Al(R10)O)n- (4)
Wherein R10For the alkyl with 1 to 10 carbon atom, a part of alkyl can be replaced by halogen and/or alkoxy；
R between repetitive unit10It can be identical or different；N is 5 or more.
The molecular structure of aikyiaiurnirsoxan beta can be straight chain or ring-type.
N value is preferably 10 or more.
R10The example of alkyl include methyl, ethyl, propyl and isobutyl group.In particular it is preferred to methyl.It can be used alone
One kind of alkyl, or two or more combinations can be used.As the alkyl of R, the preferably combination of methyl and isobutyl group.
Aforementioned aikyiaiurnirsoxan beta has low-solubility with highly dissoluble preferably in aliphatic hydrocarbon and preferably in aromatic hydrocarbon.Example
Such as, preferably as the aikyiaiurnirsoxan beta of hexane solution being obtained commercially.
The example of aliphatic hydrocarbon includes hexane and hexamethylene.
Particularly, component (D) can be the modified alumoxane (TMAO) indicated by formula (5):
-(Al(CH3)x(i-C4H9)yO)m- (5)
Wherein in formula (5), x+y 1 and m are 5 or more.
The example of TMAO includes TMAO341, is manufactured by Tosoh Finechem Corporation.
Component (D) can be the modified alumoxane (MMAO) indicated by formula (6):
-(Al(CH3)0.7(i-C4H9)0.3O)k- (6)
Wherein k is 5 or more.
The example of MMAO includes MMAO-3A, is manufactured by Tosoh Finechem Corporation.
In addition, particularly, component (D) can be the modified alumoxane (PMAO) indicated by formula (7):
-[(CH3)AlO]i- (7)
Wherein, i is 5 or more.
The example of PMAO includes TMAO-211, is manufactured by Tosoh Finechem Corporation.
For the active increase effect of fortifying catalytic, in aforementioned MMAO, TMAO and PMAO, component (D) is preferably MMAO
Or TMAO.Particularly, for the active increase effect of further fortifying catalytic, component (D) is preferably TMAO.
-- halogen compounds (component (E)) --
Component (E) is selected from by for lewis acidic halide-containing (compound (E-1)), metal halide and Louis
The group of the complex (compound (E-2)) of alkali and organic compound (compound (the E-3)) composition including reactive halogen
At least one compound.
These compounds are reacted with compound (A), that is, with M-N key containing the compound of rare earth element or this contain it is dilute
The compound of earth elements is reacted with the reaction product of lewis base, to generate cationic transition metal compound, halogenation
Metallic compound is crossed, and/or in the transistion metal compound in the insufficient state of transition metal centre charge.
By using component (E), cis--Isosorbide-5-Nitrae-linkage content of conjugated diolefin polymer can be improved.
The example of component (E-1) includes halide-containing, and the halide-containing includes the 3rd race, the 4th race, the 5th race, the 6th
The element of race, the 8th race, the 13rd race, the 14th race or the 15th race.In particular it is preferred to the halide of aluminium or the halide of organic metal.
Example for lewis acidic halide-containing include titanium tetrachloride, tungsten hexachloride, three (pentafluorophenyl group) borates,
Methyl aluminum dibromide, methylaluminum dichloride, ethyl aluminum dibromide, ethylaluminum dichloride, butyl aluminum dibromide, butyl dichloride
Aluminium, dimethyl aluminium bromide, dimethylaluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide, dibutyl chlorine
Change aluminium, sesquialter methyl bromide aluminium (methylaluminum sesquibromide), sesquialter methyl chloride aluminium, sesquialter ethyl phosphonium bromide
Aluminium, sesquialter ethylmercury chloride aluminium, alchlor, three (pentafluorophenyl group) aluminium, dibutyl tin dichloride, tin tetrachloride, phosphorus trichloride, five
Phosphorus chloride, antimony trichloride and Antimony pentachloride.In particular it is preferred to ethylaluminum dichloride, ethyl aluminum dibromide, diethyl aluminum chloride,
Diethyl aluminum bromide, sesquialter ethylmercury chloride aluminium and sesquialter ethyl phosphonium bromide aluminium.
Chlorine or bromine is preferably as halogen.
It can be used alone as one kind of lewis acidic halide-containing, or two or more combinations can be used.
The example of metal halide for component (E-2) includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, bromination
Magnesium, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, chlorination
Cadmium, cadmium bromide, cadmium iodide, mercury chloride, mercuric bromide, mercuric iodixde, manganese chloride, manganous bromide, manganese iodide, chlorination rhenium, bromination rhenium, iodate
Rhenium, copper chloride, cupric iodide, silver chlorate, silver bromide, silver iodide, chlorauride, auric iodide and gold bromide.In these, preferably chlorination
Magnesium, calcium chloride, barium chloride, zinc chloride, manganese chloride and copper chloride, particularly preferred magnesium chloride, zinc chloride, manganese chloride and copper chloride.
The preferred phosphorus compound of lewis base, carbonyls, nitrogen compound, ether compound or alcohol for component (E-2)
Deng.
Example includes tributyl phosphate, tricresyl phosphate -2- ethylhexyl, triphenyl phosphate, tricresyl phosphate
(tricresyl phosphate), triethyl phosphine, tributylphosphine, triphenylphosphine, diethylphosphino ethane, diphenylphosphino second
Alkane, acetylacetone,2,4-pentanedione, benzoyl acetone, propionitrile acetone, valeryl benzylacetone, ethylacetoacetone, methyl acetoacetate, acetoacetate
Ethyl ester, acetoacetate phenyl ester, dimethyl malenate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2- ethyl hexyl
Acid, oleic acid, stearic acid, benzoic acid, aphthenic acids, versatic acid (versatic acid), triethylamine, DMAC N,N' dimethyl acetamide, four
Hydrogen furans, diphenyl ether, 2-Ethylhexyl Alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1- decyl alcohol and laruyl alcohol etc..In particular it is preferred to
Tricresyl phosphate -2- ethylhexyl, tricresyl phosphate, acetylacetone,2,4-pentanedione, 2 ethyl hexanoic acid, versatic acid, 2-Ethylhexyl Alcohol, 1- decyl alcohol and
Laruyl alcohol.
The molal quantity of lewis base is with every mole metal halide for 0.01 mole to 30 moles, preferably 0.5 mole to 10
Mole ratio reaction.Use with the reaction product of lewis base reduces the metal of residual in the polymer.
The example of component (E-3) includes benzyl chloride.
Weight ratio between component in example polymerization catalyst composition is described below.
In order to obtain sufficient catalytic activity, component (B) (compound with cyclopentadienyl skeleton) is (dilute with component (A)
Earth elements compound) molar ratio be preferably greater than zero, more preferable 0.5 or more, particularly preferred 1 or more.In order to inhibit catalytic activity
Reduction, this is than preferably 3 hereinafter, more preferable 2.5 hereinafter, particularly preferred 2.2 or less.
In order to improve the catalytic activity in reaction system, the molar ratio of component (C) (organo-metallic compound) and component (A)
It is preferred that 1 or more, more preferable 5 or more.In order to inhibit the reduction of catalytic activity in reaction system, this is than being preferably 50 hereinafter, more excellent
Select 30 hereinafter, particularly preferably about 10.
Rare earth member in order to improve the catalytic activity in reaction system, in the aluminium and component (A) in component (D) (aikyiaiurnirsoxan beta)
The molar ratio of element is preferably 10 or more, and more preferable 100 or more.In order to inhibit the reduction of catalytic activity in reaction system, this is than excellent
It selects 1000 hereinafter, more preferable 800 or less.
In order to improve catalytic activity, the molar ratio preferably zero or more of component (E) (halogen compounds) and component (A) is more excellent
Select 0.5 or more, particularly preferred 1.0 or more.In order to maintain the dissolubility of component (E) and inhibit the reduction of catalytic activity, this is than excellent
20 are selected as hereinafter, more preferable 10 or less.
Therefore, within the above range, the cis--Isosorbide-5-Nitrae-linkage content effect for improving conjugated diolefin polymer can be improved.
Example polymerization catalyst composition it is preferably not included that by non-coordinating anion (such as tetravalent boron anion) and sun from
Son is (for example, carbocation (carbonium cation), oxygen cation (oxonium cation), ammonium cation, Phosphonium sun
Ion, cycloheptatriene base cation and the ferrocene cation with transition metal) composition ionic compound.Ionicization
Close object has low-solubility with highly dissoluble in aromatic hydrocarbon and in hydrocarbon.Therefore, by using not including ionic chemical combination
The polymerization catalyst composition of object can manufacture polymerization of conjugated dienes while being further reduced environmental pressure and manufacturing cost
Object.
Statement " not including ionic compound " refers to that ionic compound includes the ratio in polymerization catalyst composition
Example is less than 0.01wt%.
Conjugate diene monomer-
The example of the conjugate diene monomer of the example manufacturing process of conjugated diolefin polymer for the disclosure includes 1,3-
Butadiene, isoprene, 1,3- pentadiene, 2,3- dimethyl -1,3- butadiene and 1,3- hexadiene.Particularly, in order to improve
The various characteristics of rubber composition and tire etc., preferably 1,3-butadiene and isoprene.
It can be used alone one of these, or two or more combinations can be used.
Particularly, when conjugate diene monomer is isoprene and 1,3-butadiene, then in order to improve in reaction system
Catalytic activity simultaneously reduces molecular weight distribution, and the ratio between isoprene and 1,3-butadiene are preferably 1 or more, more preferable 3 or more, especially
It is preferred that 7 or more.
Reagent for each process can use under solvent-free or under the solvent for being suitable for various reagents.
In each process, reagent and solvent after distillation, degassing and freeze-drying etc. preferably in appropriate purifying for example, make
With.
In foregoing sequence, especially catalyst system preparation section and polymerization reaction process, preferably in inert gas atmosphere
As carried out under nitrogen or argon gas.
In order to obtain sufficient catalytic activity, component (A) is preferably relative to the mole of 100g conjugate diene monomer
0.01mmol or more, more preferable 0.03mmol or more, excessively catalysis in order to prevent, preferably 0.5mmol is hereinafter, more preferably
0.05mmol or less.
Any solvent inert in the polymerization can be used.Example includes n-hexane, hexamethylene and its mixture.
The aromatic hydrocarbon (benzene, toluene or dimethylbenzene etc.) of strong toxicity is not required.
In polymerization reaction process, any known method in the art, such as polymerisation in solution, suspension can be used
Polymerization, liquid-phase bulk polymerization, emulsion polymerization, gas-phase polymerization or solid phase.
Reaction temperature can be any temperature, such as -100 DEG C to 300 DEG C, preferably 0 DEG C to 200 DEG C, more preferable 25 DEG C to 120
℃.Under high temperature, cis--Isosorbide-5-Nitrae-selectivity be may deteriorate, and under low temperature, reaction speed may be decreased.
Reaction pressure can be any pressure, such as normal pressure.Under high pressure, conjugate diene monomer may not sufficiently be incorporated to poly-
Reaction system is closed, and under low pressure, reaction speed may be decreased.
Reaction time can be any time, such as 30 minutes to 3 hours.
The manufacturing method of the conjugated diolefin polymer of the disclosure is not limited to previous examples manufacturing method.For example, in aforementioned reality
In example manufacturing method, the compound with cyclopentadienyl skeleton can add in polymerization reaction process, instead of in caltalyst
It is to be included in polymerization catalyst composition in preparation section.
(conjugated diolefin polymer)
The example manufacturing process of conjugated diolefin polymer according to the disclosure manufactures the conjugated diolefin polymer of the disclosure
Example (example conjugated diolefin polymer).
Example conjugated diolefin polymer has 95% or more high cis- -1,4- linkage content.It is, therefore, possible to provide having
Enrich the conjugated diolefin polymer of elasticity, and the rubber components that can be used as in rubber composition.
Example conjugated diolefin polymer can be the homopolymer of conjugate diene monomer or can be copolymer.
Cis--Isosorbide-5-Nitrae-linkage content of example conjugated diolefin polymer is 95% or more, preferably 97% or more, even more preferably
98% or more.As the value is higher, the elongation induction crystallinity (elongation-induced of conjugated diolefin polymer can be increased
Crystallization ability) and the elasticity of conjugated diolefin polymer can be increased.
Anti-form-1,4- linkage content can be arbitrary value but preferably smaller than 5%, more preferably less than 3%, particularly preferably less than 1%.
As the value is lower, the elongation induction crystallinity of conjugated diolefin polymer can be increased and the bullet of conjugated diolefin polymer can be increased
Property.
1,2- vinyl bond content can for arbitrary value but preferably 5% or less, more preferable 3% or less, particularly preferred 1% with
Under.As the value is lower, the elongation induction crystallinity of isoprene-butadiene block copolymer can be increased and total isoamyl can be increased
Diene-butadiene block copolymer elasticity.
3,4- vinyl bond content can for arbitrary value but preferably 5% or less, more preferable 3% or less, particularly preferred 1% with
Under.As the value is lower, the elongation induction crystallinity of conjugated diolefin polymer can be increased and the bullet of yoke diene polymer can be increased
Property.
The number-average molecular weight (Mn) preferably 400,000 or more, more preferable 500,000 or more of example conjugated diolefin polymer.
Molecular weight distribution (Mw/Mn) preferably 3 is hereinafter, more preferable 2 or less.
The example of conjugated diolefin polymer include polybutadiene, polyisoprene, polyprene, polydimethyl butadiene and
Poly- hexadiene.Particularly, in order to improve the various characteristics of rubber composition and tire etc., preferably polybutadiene and poly- isoamyl two
Alkene.
The manufacturing method of the conjugated diolefin polymer of the present embodiment can be by isoprene and 1,3- butadiene copolymer
Isoprene-butadiene block copolymer manufacturing method.
The example that the manufacturing method of the isoprene-butadiene block copolymer of the disclosure is described below.
Example (the example system of block copolymer of the manufacturing method of the isoprene-butadiene block copolymer of the disclosure
Make method) it is the side for coming copolymerised isoprene and 1,3- butadiene using the example polymerization catalyst composition of the above-mentioned disclosure
Method.
Specifically, the example manufacturing process of block copolymer includes:
Prepare the monomer preparatory process of isoprene and 1,3- butadiene；
Prepare the catalyst system preparation section of the example polymerization catalyst composition of the above-mentioned disclosure；With
Including mixing and polymerizeing polymerization catalyst composition and the first monomer (one of isoprene and 1,3- butadiene)
First polymerization reaction process of first monomer and after the first polymerization reaction process add second comonomer (isoprene and 1,
The other of 3- butadiene) and polymerize the second comonomer the second polymerization reaction process copolyreaction process.
In the example manufacturing process of the block copolymer, firstly, preparing the example polymerization catalyst group of the above-mentioned disclosure
Close object.It then, include rare earth element in preparation by mixing isoprene and 1,3-butadiene with polymerization catalyst composition
Being total to for isoprene and 1,3- butadiene is realized while the reaction system of compound and compound with cyclopentadienyl skeleton
It is poly-.
Monomer preparatory process-
The isoprene and 1,3-butadiene prepared in monomer preparatory process be not particularly limited, and can be used and is obtained commercially
Isoprene and 1,3- butadiene.
Catalyst system preparation section-
The polymerization catalyst composition prepared in catalyst system preparation section is described below.
-- polymerization catalyst composition --
The example (example polymerization catalyst composition) of polymerization catalyst composition for the disclosure is as described above.
Copolyreaction process-
In copolyreaction process, well known method any in the art, such as polymerisation in solution, suspension can be used
Polymerization, liquid-phase bulk polymerization, emulsion polymerization, gas-phase polymerization or solid phase.
Reaction temperature can be any temperature, such as -80 DEG C to 100 DEG C, preferably 10 DEG C to 80 DEG C, more preferable 25 DEG C to 50
℃.Under high temperature, cis--Isosorbide-5-Nitrae-selectivity be may deteriorate, and under low temperature, reaction speed may be decreased.
Reaction time can be any time, such as 30 minutes to 3 hours.
In order to improve the catalytic activity in reaction system and reduce molecular weight distribution, the ratio between isoprene and 1,3-butadiene
It is preferred that 1 or more, more preferable 3 or more, particularly preferred 7 or more.
In order to obtain sufficient catalytic activity, component (A) is relative to 100g the first monomer (isoprene and 1,3-butadiene
One of) mole be preferably 0.01mmol or more, more preferable 0.03mmol or more, in order to prevent excessively catalysis, preferably
0.5mmol is hereinafter, more preferably 0.05mmol or less.
Reagent for each process can use under solvent-free or under the solvent for being suitable for various reagents.
In each process, reagent and solvent after distillation, degassing and freeze-drying etc. preferably in appropriate purifying for example, make
With.
In foregoing sequence, especially catalyst system preparation section and polymerization reaction process, preferably in inert gas atmosphere
As carried out under nitrogen or argon gas.
As the solvent in the example manufacturing process for block copolymer, can be used inert in the polymerization
Any solvent.Example includes n-hexane, hexamethylene and its mixture.The aromatic hydrocarbon (benzene, toluene or dimethylbenzene etc.) of strong toxicity is no
It is required.
The manufacturing method of the isoprene-butadiene block copolymer of the disclosure is not limited to previous examples manufacturing method.Example
Such as, in previous examples manufacturing method, the compound with cyclopentadienyl skeleton can add in copolyreaction process, instead of
It is included in polymerization catalyst composition in catalyst system preparation section.
(isoprene-butadiene block copolymer)
The example (example block copolymer) of the isoprene-butadiene block copolymer of the disclosure is different by the disclosure
The manufacture of pentadiene-butadiene block copolymer example manufacturing process.
Example block copolymer has 98% or more high cis- -1,4- linkage content.It is, therefore, possible to provide having abundant
The isoprene-butadiene block copolymer of elasticity, and the rubber components that can be used as in rubber composition.
The structure of block copolymer is (A-B) x, A- (B-A) x and B- (A-B) x (wherein, A be by isoprene monomer list
The block section (block sequence) that member is constituted, B be the block section being made of 1,3-butadiene monomeric unit, x for 1 with
On integer) one of.Block copolymer containing multiple (A-B) or (B-A) structure is referred to as segmented copolymer.
The content of the part from isoprene in example block copolymer is preferably 20% or more, more preferable 50% with
On.On the other hand, the content preferably 80% of the part in isoprene-butadiene block copolymer from butadiene is hereinafter, more
It is preferred that 50% or less.These contents indicate the molar ratio relative to block copolymer entirety.
Cis--Isosorbide-5-Nitrae-linkage content of part in example block copolymer from isoprene is 98.0% or more, preferably
98.5% or more, even more preferably 99.0% or more.As the value is higher, isoprene-butadiene block copolymer can be increased
Elongation induction crystallinity and the elasticity of isoprene-butadiene block copolymer can be increased.
The anti-form-1 of part from isoprene, 4- linkage content can be arbitrary value, but preferably smaller than 2.0%, more preferably
Less than 1.5%, particularly preferably less than 1.0%.As the value is lower, stretching for isoprene-butadiene block copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene block copolymer can be increased.
1, the 2- vinyl bond content of part from isoprene can be arbitrary value, but preferably 2.0% hereinafter, more preferably
1.5% hereinafter, particularly preferred 1.0% or less.As the value is lower, stretching for isoprene-butadiene block copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene block copolymer can be increased.
3, the 4- vinyl bond content of part from isoprene can be arbitrary value, but preferably 2.0% hereinafter, more preferably
1.5% hereinafter, particularly preferred 1.0% or less.As the value is lower, stretching for isoprene-butadiene block copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene block copolymer can be increased.
Above-mentioned cis- -1,4- linkage content, anti-form-1,4- linkage content, 1,2- vinyl bond content and 3,4- vinyl bonds
Content does not imply that the ratio relative to block copolymer entirety, but the amount in the part for being originated from isoprene.
Cis--Isosorbide-5-Nitrae-linkage content of part in example block copolymer from butadiene is 98% or more, preferably
98.5% or more, even more preferably 99% or more.As the value is higher, isoprene-butadiene block copolymer can be increased
Elongation induction crystallinity and the elasticity that isoprene-butadiene block copolymer can be increased.
The anti-form-1 of part from butadiene, 4- linkage content can be arbitrary value, but preferably smaller than 5%, more preferably less than
3%, particularly preferably less than 1%.As the value is lower, the elongation induction knot of isoprene-butadiene block copolymer can be increased
Crystalline substance and the elasticity that isoprene-butadiene block copolymer can be increased.
The vinyl bond content of part from butadiene can be arbitrary value, but preferably 5% hereinafter, more preferable 3% hereinafter,
Particularly preferred 1% or less.As the value is lower, the elongation induction crystallinity of isoprene-butadiene block copolymer can be increased
And the elasticity of isoprene-butadiene block copolymer can be increased.
Above-mentioned cis- -1,4- linkage content, anti-form-1,4- linkage content and vinyl bond content are not implied that relative to block
The ratio of copolymer entirety, but the amount in the part for being originated from butadiene.
When in example block copolymer referred to as " cis- -1,4- linkage content " without specified isoprenyl moiety or fourth
When diene portions, cis--Isosorbide-5-Nitrae-linkage content in isoprene-butadiene block copolymer entirety is referred to.
The number-average molecular weight (Mn) preferably 50,000 to 6,000,000, more preferable 1,000,000 of example block copolymer to
3,000,000。
Molecular weight distribution (Mw/Mn) preferably 4 is hereinafter, more preferable 3 or less.
The manufacturing method of the conjugated diolefin polymer of the present embodiment can be by isoprene and 1,3- butadiene copolymer
The manufacturing method of isoprene-butadiene random copolymer.
The example that the manufacturing method of the isoprene-butadiene random copolymer of the disclosure is described below.
Example (the example system of random copolymer of the manufacturing method of the isoprene-butadiene random copolymer of the disclosure
Make method) it needs to come copolymerised isoprene and 1,3- butadiene using the example polymerization catalyst composition of the above-mentioned disclosure.
Specifically, the example manufacturing process of random copolymer includes:
Prepare the monomer preparatory process of isoprene and 1,3- butadiene；
Prepare the catalyst system preparation section of the example polymerization catalyst composition of the above-mentioned disclosure；With
Including polymerization catalyst composition to be mixed to simultaneously polymerized isoprene and 1,3- with isoprene and 1,3- butadiene
The copolyreaction process (atactic polymerization) of butadiene.
In the example manufacturing process of this random copolymer, the example polymerization catalyst combination of the above-mentioned disclosure is prepared first
Object.It then, include rare earth element in preparation by mixing isoprene and 1,3-butadiene with polymerization catalyst composition
The copolymerization of isoprene and 1,3- butadiene is realized while the reaction system of conjunction object and the compound with cyclopentadienyl skeleton.
Monomer preparatory process-
The isoprene and 1,3-butadiene prepared in monomer preparatory process be not particularly limited, and can be used and is obtained commercially
Isoprene and 1,3- butadiene.
Catalyst system preparation section-
The polymerization catalyst composition prepared in catalyst system preparation section is described below.
-- polymerization catalyst composition --
The example (example polymerization catalyst composition) of polymerization catalyst composition for the disclosure is as described above.
Copolyreaction process-
In copolyreaction process, well known method any in the art, such as polymerisation in solution, suspension can be used
Polymerization, liquid-phase bulk polymerization, emulsion polymerization, gas-phase polymerization or solid phase.
Reaction temperature can be any temperature, such as -80 DEG C to 100 DEG C, preferably 10 DEG C to 80 DEG C, more preferable 25 DEG C to 50
℃.Under high temperature, cis--Isosorbide-5-Nitrae-selectivity be may deteriorate, and under low temperature, reaction speed may be decreased.
Reaction time can be any time, such as 30 minutes to 3 hours.
In order to improve the catalytic activity in reaction system and reduce molecular weight distribution, the ratio between isoprene and 1,3-butadiene
It is preferred that 1 or more, more preferable 3 or more, particularly preferred 7 or more.
In order to obtain sufficient catalytic activity, component (A) is relative to 100g total monomer amount (isoprene and 1,3-butadiene
Total amount) mole be preferably 0.01mmol or more, more preferable 0.03mmol or more, in order to prevent excessively catalysis, preferably
0.5mmol is hereinafter, more preferably 0.05mmol or less.
Reagent for each process can use under solvent-free or under the solvent for being suitable for various reagents.
In each process, reagent and solvent after distillation, degassing and freeze-drying etc. preferably in appropriate purifying for example, make
With.
In foregoing sequence, especially catalyst system preparation section and polymerization reaction process, preferably in inert gas atmosphere
As carried out under nitrogen or argon gas.
As the solvent in the example manufacturing process for random copolymer, can be used inert in the polymerization
Any solvent.Example includes n-hexane, hexamethylene and its mixture.The aromatic hydrocarbon (benzene, toluene or dimethylbenzene etc.) of strong toxicity is no
It is required.
The manufacturing method of the isoprene-butadiene random copolymer of the disclosure is not limited to previous examples manufacturing method.Example
Such as, in previous examples manufacturing method, the compound with cyclopentadienyl skeleton can add in copolyreaction process, instead of
It is included in polymerization catalyst composition in catalyst system preparation section.
(isoprene-butadiene random copolymer)
The example (example random copolymer) of the isoprene-butadiene random copolymer of the disclosure is different by the disclosure
The manufacture of pentadiene-butadiene random copolymer example manufacturing process.
Example random copolymer has 98% or more high cis- -1,4- linkage content.It is, therefore, possible to provide having abundant
The isoprene-butadiene random copolymer of elasticity, and the rubber components that can be used as in rubber composition.
In random copolymer, the sequence of isoprene and 1,3-butadiene monomeric unit is irregular.
The content of the part from isoprene in example random copolymer is preferably 20% or more, more preferable 50% with
On.On the other hand, the content preferably 80% of the part in isoprene-butadiene random copolymer from butadiene is hereinafter, more
It is preferred that 50% or less.These contents indicate the molar ratio relative to random copolymer entirety.
Cis--Isosorbide-5-Nitrae-linkage content of part in example random copolymer from isoprene is 98.0% or more, preferably
98.5% or more, even more preferably 99.0% or more.As the value is higher, isoprene-butadiene random copolymer can be increased
Elongation induction crystallinity and the elasticity of isoprene-butadiene random copolymer can be increased.
The anti-form-1 of part from isoprene, 4- linkage content can be arbitrary value, but preferably smaller than 2.0%, more preferably
Less than 1.5%, particularly preferably less than 1.0%.As the value is lower, stretching for isoprene-butadiene random copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene random copolymer can be increased.
1, the 2- vinyl bond content of part from isoprene can be arbitrary value, but preferably 2.0% hereinafter, more preferably
1.5% hereinafter, particularly preferred 1.0% or less.As the value is lower, stretching for isoprene-butadiene random copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene random copolymer can be increased.
3, the 4- vinyl bond content of part from isoprene can be arbitrary value, but preferably 2.0% hereinafter, more preferably
1.5% hereinafter, particularly preferred 1.0% or less.As the value is lower, stretching for isoprene-butadiene random copolymer can be increased
Long induction crystallinity and the elasticity that isoprene-butadiene random copolymer can be increased.
Above-mentioned cis- -1,4- linkage content, anti-form-1,4- linkage content, 1,2- vinyl bond content and 3,4- vinyl bonds
Content does not imply that the ratio relative to random copolymer entirety, but the amount in the part for being originated from isoprene.
Cis--Isosorbide-5-Nitrae-linkage content of part in example random copolymer from butadiene is 98% or more, preferably
98.5% or more, even more preferably 99% or more.As the value is higher, isoprene-butadiene random copolymer can be increased
Elongation induction crystallinity and the elasticity that isoprene-butadiene random copolymer can be increased.
The anti-form-1 of part from butadiene, 4- linkage content can be arbitrary value, but preferably smaller than 5%, more preferably less than
3%, particularly preferably less than 1%.As the value is lower, the elongation induction knot of isoprene-butadiene random copolymer can be increased
Crystalline substance and the elasticity that isoprene-butadiene random copolymer can be increased.
The vinyl bond content of part from butadiene can be arbitrary value, but preferably 5% hereinafter, more preferable 3% hereinafter,
Particularly preferred 1% or less.As the value is lower, the elongation induction crystallinity of isoprene-butadiene random copolymer can be increased
And the elasticity of isoprene-butadiene random copolymer can be increased.
Above-mentioned cis- -1,4- linkage content, anti-form-1,4- linkage content and vinyl bond content are not implied that relative to random
The ratio of copolymer entirety, but the amount in the part for being originated from butadiene.
When in example random copolymer referred to as " cis- -1,4- linkage content " without specified isoprenyl moiety or fourth
When diene portions, cis--Isosorbide-5-Nitrae-linkage content in isoprene-butadiene random copolymer entirety is referred to.
The number-average molecular weight (Mn) preferably 50,000 to 6,000,000, more preferable 1,000,000 of example random copolymer to
3,000,000。
Molecular weight distribution (Mw/Mn) preferably 4 is hereinafter, more preferable 3 or less.
(rubber composition)
The example (example rubber composition) of the rubber composition of the disclosure need include the disclosure example conjugated diene
Polymer.The example conjugated diolefin polymer of the disclosure can be rubber components.
Example rubber composition may include the rubber components in addition to example conjugated diolefin polymer and can also wrap
Include filler, anti-aging agent, softening agent, stearic acid, zinc oxide, vulcanization accelerator, vulcanizing agent, oil or sulphur etc..
Example rubber composition can use method manufacture known to persons of ordinary skill in the art.
(tire)
The example (example tire) of the tire of the disclosure needs to manufacture using the example rubber composition of the disclosure.Example wheel
The manufacture of example rubber composition can be used in all components of tire.
Example tire can use method manufacture known to persons of ordinary skill in the art.
Example rubber composition can be used also to manufacture in rubber product such as shoes, band and floor in addition to tire etc..
Embodiment
The disclosure is more fully described below with reference to embodiment, the disclosure is never intended to be limited.
(manufacture of conjugated diolefin polymer)
Conjugated diolefin polymer is manufactured according to following experiments item.
(embodiment A1)
Firstly, will be added including the hexane solution 800g of 120g (1.76mol) isoprene (conjugate diene monomer) abundant
In dry stainless steel 2L reactor.
On the other hand, by 70.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 140.0 μm of ol 2- phenylindans (component (B)) and 0.70mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen
The glass container in glove box under atmosphere is simultaneously dissolved in 30mL hexane.Then by MMAO (MMAO-3A, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in MMAO
The molar ratio of gadolinium be 200 to be added to glass container.Then 140.0 μm of ol diethyl aluminum chloride (component (E- are further added
1)), to generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 60.0 μm of ol gadoliniums
Agent composition is added to the 2L reactor including isoprene.The reaction system is maintained at 50 DEG C 60 minutes, and is carried out
The polymerization reaction of isoprene.Then, by 2,2'- methylene-bis- (6- tert-butyl -4- ethyl -phenols) (Nocrac NS-5, by
Ouchi Shinko Chemical Industrial Co., Ltd. manufacture) aqueous isopropanol (5 mass %) 5mL be added to
Reaction system is to terminate polymerization reaction.In addition, precipitating and separating reaction product by adding a large amount of methanol to reactor.Then
Gains are dried in vacuo at 60 DEG C, to obtain polymer AA (yield: 116g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment A2)
Other than using 3- benzyl indenes to replace 2- phenylindan, polymerization catalyst is prepared in a manner of identical with embodiment A1
Composition simultaneously carries out polymerization reaction, to obtain polymer AB (yield: 116g).
(embodiment A3)
Other than using indenes to replace 2- phenylindan, polymerization catalyst composition is prepared in a manner of identical with embodiment A1
And polymerization reaction is carried out, to obtain polymer AC (yield: 105g).
(Comparative examples A 1)
Reaction system maintained at 50 DEG C other than 180 minutes in addition to without using 2- phenyl indeno, with embodiment A1 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer AD (yield: 60g).
(Comparative examples A 2)
In addition to using bis- (the dimetylsilyl amide) ((2-PhC of bis- (2- phenyl indenyl) gadoliniums9H6)2GdN(SiHMe2)2)
(metallocene catalyst) replaces three (double-trimethylsilylamide) gadoliniums and 2- phenyl indeno that reaction system is maintained 50 DEG C
Other than lower 180 minutes, polymerization catalyst composition is prepared in a manner of identical with embodiment A1 and carries out polymerization reaction, thus
To polymer AE (yield: 75g).
(embodiment A4)
Firstly, the hexane solution 800g addition including 150g (2.78mol) 1,3-butadiene (conjugate diene monomer) is filled
Divide in dry stainless steel 2L reactor.
On the other hand, by 15.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 45.0 μm of ol 3- benzyl indenes (component (B)) and 0.018mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen
The glass container in glove box under atmosphere is simultaneously dissolved in 10mL hexane.Then by MMAO (MMAO-3A, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in MMAO
The molar ratio of gadolinium be 500 to be added to glass container.Then 30.0 μm of ol diethyl aluminum chloride (component (E- are further added
1)), to generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 15.0 μm of ol gadoliniums
Agent composition is added to the 2L reactor including 1,3- butadiene.The reaction system is maintained at 60 DEG C 60 minutes, is gone forward side by side
The polymerization reaction of row 1,3- butadiene.Then, by bis- (6- tert-butyl -4- ethyl -phenol) (the Nocrac NS- of 2,2'- methylene -
5, by Ouchi Shinko Chemical Industrial Co., Ltd. manufacture) aqueous isopropanol (5 mass %) 5mL add
Reaction system is added to terminate polymerization reaction.In addition, precipitating and separating reaction product by adding a large amount of methanol to reactor.
Then gains are dried in vacuo at 60 DEG C, to obtain polymer AF (yield: 116g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment A5)
In addition to using TMAO (TMAO-341 is manufactured by Tosoh Finechem Corporation) to replace other than MMAO,
Polymerization catalyst composition is prepared in a manner of identical with embodiment A4 and carries out polymerization reaction, (is produced to obtain polymer AG
Amount: 145g).
(embodiment A6)
Other than using 2- phenylindan to replace 3- benzyl indenes, polymerization catalyst is prepared in a manner of identical with embodiment A4
Composition simultaneously carries out polymerization reaction, to obtain polymer AH (yield: 145g).
(embodiment A7)
Other than using 3- methyl -2- phenylindan to replace 3- benzyl indenes, prepared in a manner of identical with embodiment A4 poly-
It closes carbon monoxide-olefin polymeric and carries out polymerization reaction, to obtain polymer AI (yield: 105g).
(embodiment A8)
Other than using 3- benzyl -2- phenylindan to replace 3- benzyl indenes, prepared in a manner of identical with embodiment A4 poly-
It closes carbon monoxide-olefin polymeric and carries out polymerization reaction, to obtain polymer AJ (yield: 105g).
(embodiment A9)
Other than using indenes to replace 3- benzyl indenes, polymerization catalyst composition is prepared in a manner of identical with embodiment A4
And polymerization reaction is carried out, to obtain polymer AK (yield: 105g).
(Comparative examples A 3)
Reaction system maintained at 60 DEG C other than 180 minutes in addition to without using 3- benzyl indeno, with embodiment A4 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer AL (yield: 60g).
(embodiment A10)
In addition to using PMAO (TMAO-211, by Tosoh Finechem Corporation manufacture) to replace MMAO and will be anti-
It answers system to maintain at 60 DEG C other than 180 minutes, prepares polymerization catalyst composition in a manner of identical with embodiment A4 and go forward side by side
Row polymerization reaction, to obtain polymer AM (yield: 30g).
(embodiment A11)
Firstly, will be added including the hexane solution 400mL of the 1,3-butadiene (conjugate diene monomer) of 70g (1.29mol)
Sufficiently in dry stainless steel 2L reactor.
On the other hand, by 50.4 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 100.0 μm of ol 3- benzyl indenes (component (B)) and 0.75mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen
The glass container in glove box under atmosphere is simultaneously dissolved in 30mL hexane.Then by TMAO (TMAO341, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in TMAO
The molar ratio of gadolinium be 67 to be added to glass container.Then 25.2 μm of ol diethyl aluminum chlorides (component (E-1)) are further added,
To generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 40.0 μm of ol gadoliniums
Agent composition is added to the 2L reactor including 1,3- butadiene.The reaction system is maintained at 50 DEG C 40 minutes, is gone forward side by side
The polymerization reaction of row 1,3- butadiene.Then, by bis- (6- tert-butyl -4- ethyl -phenol) (the Nocrac NS- of 2,2'- methylene -
5, by Ouchi Shinko Chemical Industrial Co., Ltd. manufacture) aqueous isopropanol (5 mass %) 1mL add
Reaction system is added to terminate polymerization reaction.In addition, being produced by adding a large amount of isopropanols to reactor to precipitate and separate reaction
Object.Then gains are dried in vacuo at 60 DEG C, to obtain polymer AN (yield: 66g).
(embodiment A12 to embodiment A15)
In addition to the additive amount of diethyl aluminum chloride is set as 50.4 μm of ol (embodiment A12), 100.8 μm of ol (embodiments
A13), other than 504 μm of ol (embodiment A14) and 1008 μm of ol (embodiment A15), prepared in a manner of identical with embodiment A11
Polymerization catalyst composition simultaneously carries out polymerization reaction, to obtain polymer AO to AR, (yield: 66g in embodiment A12 is implemented
65g in 66g and embodiment A15 in 67g in example A13, embodiment A14).
(embodiment A16)
Other than not adding diethyl aluminum chloride, polymerization catalyst is prepared in a manner of identical with embodiment A11 and is combined
Object simultaneously carries out polymerization reaction, to obtain polymer AS (yield: 60g).
(embodiment A17)
Firstly, will be added including the hexane solution 550g of the 1,3-butadiene (conjugate diene monomer) of 100g (1.85mol)
Sufficiently in dry stainless steel 2L reactor.
On the other hand, by 15.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 30.0 μm of ol 2- phenylindans (component (B)), 0.60mmol diisobutyl aluminium hydride (component (C)) and tri- isobutyl of 6.0mol
Glass container that base aluminium (component (C)) is added in glove box in a nitrogen atmosphere is simultaneously dissolved in 10mL hexane.Then will
MMAO (MMAO-3A is manufactured by Tosoh Finechem Corporation) (component (D)) is with the aluminium and three (double-three in MMAO
Methyl silicane base amide) molar ratio of gadolinium in gadolinium is 400 to be added to glass container, to generate polymerization catalyst combination
Object.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 10.0 μm of ol gadoliniums
Agent composition is added to the 2L reactor including 1,3- butadiene.The reaction system is maintained at 50 DEG C 80 minutes, is gone forward side by side
The polymerization reaction of row 1,3- butadiene.Then, by bis- (6- tert-butyl -4- ethyl -phenol) (the Nocrac NS- of 2,2'- methylene -
5, by Ouchi Shinko Chemical Industrial Co., Ltd. manufacture) aqueous isopropanol (5 mass %) 5mL add
Reaction system is added to terminate polymerization reaction.In addition, precipitating and separating reaction product by adding a large amount of methanol to reactor.
Then gains are dried in vacuo at 60 DEG C, to obtain polymer AT (yield: 94g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment A18)
Other than the dosage of three (double-trimethylsilylamide) gadoliniums and 2- phenylindan is halved, with embodiment
The identical mode of A17 prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer AU (yield: 65g).
(Comparative examples A 4)
Reaction system maintained at 50 DEG C other than 180 minutes in addition to without using 2- phenyl indeno, with embodiment A17 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer AV (yield: 60g).
(Comparative examples A 5)
Other than halving the dosage of three (double-trimethylsilylamide) gadoliniums, with side identical with embodiment A17
Formula prepares polymerization catalyst composition and carries out polymerization reaction, but does not obtain polymer.
(embodiment A19)
In addition to using bis- (the dimetylsilyl amide) ((2-PhC of bis- (2- phenyl indenyl) gadoliniums9H6)2GdN(SiHMe2)2)
(metallocene catalyst) replaces three (double-trimethylsilylamide) gadoliniums and 2- phenyl indeno that reaction system is maintained 50 DEG C
Other than lower 180 minutes, polymerization catalyst composition is prepared in a manner of identical with embodiment A17 and carries out polymerization reaction, thus
Obtain polymer AX (yield: 78g).
(embodiment A20)
In addition to using Gd (OtBu)3Other than three (double-trimethylsilylamide) gadoliniums, with identical as embodiment A1
Mode prepare polymerization catalyst composition and carry out polymerization reaction, to obtain polymer AY (yield: 116g).
(embodiment A21)
In addition to using Gd (StBu)3Other than three (double-trimethylsilylamide) gadoliniums, with identical as embodiment A1
Mode prepare polymerization catalyst composition and carry out polymerization reaction, to obtain polymer AZ (yield: 116g).
The manufacture of the preparation and conjugated diolefin polymer of polymerization catalyst composition in each embodiment A and Comparative examples A
Details are listed in table 1.
It is calculate by the following formula the catalytic activity of polymerization catalyst composition during manufacturing.
(yield (kg))/((dosage (mol) of component (A)) × (reaction time (hour)))
(analysis of conjugated diolefin polymer)
The analysis of (1) and (2) is carried out to the polymer A as above obtained.
(1) analysis of micro-structure (cis- -1,4- linkage content)
Polymer A each for gained obtains H NMR spectroscopy using NMR (AVANCE 600, manufactured by Bruker).It is surveyed by passing through
Amount1H-NMR and13Peak that C-NMR is obtained (1H-NMR: δ 4.6-4.8 (3,4- vinyl units=CH2), (Isosorbide-5-Nitrae-is mono- by 5.0-5.2
- the CH=of member),13C-NMR: δ 23.4 (Isosorbide-5-Nitrae-cis units), 15.9 (Isosorbide-5-Nitraes-trans units), 18.6 (Unit 3,4-)) product
Divide ratio, calculates cis--Isosorbide-5-Nitrae-linkage content (%).
(2) analysis of number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn)
By gel permeation chromatography (GPC), (HLC-8220GPC is manufactured by Tosoh Corporation；Two columns:
TSKgel GMHXL, manufactured by Tosoh Corporation；Detector: differential refractometer (RI)), be with monodisperse polystyrene
Reference calculates number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) that polymer A is converted with polystyrene.Measuring temperature is
40 DEG C, eluting solvent THF.
The details of the analysis result of conjugated diolefin polymer are listed in table 1 in each embodiment A and Comparative examples A.
Embodiment A1 to A21 and Comparative examples A 1 to the comparison between A5 are shown including the compound with cyclopentadienyl skeleton
The disclosure polymerization catalyst composition, compared with the polymerization catalyst composition for not including the compound, generate it is higher
Catalytic activity.Therefore, embodiment A1 to A21 obtains the desired effects of the application.
In addition, the comparison between embodiment A1 to A21 and Comparative examples A 2 shows the polymerization catalyst composition of the disclosure, with
Known case includes the catalyst that is made of the metallocene cationoid complex of gadolinium compound as major catalyst but does not wrap
It includes the compound with cyclopentadienyl skeleton to compare, better dissolubility and higher catalysis is generated in high aliphatic hydrocarbon (hexane)
Activity.Therefore, embodiment A1 to A21 obtains the desired effects of the application.
(manufacture of isoprene-butadiene block copolymer)
Isoprene-butadiene block copolymer is manufactured according to following experiments item.
(embodiment B1)
Firstly, sufficiently dry stainless steel 1L will be added including the hexane solution 200g of the isoprene of 30g (0.44mol)
In reactor.
On the other hand, by 39.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 78.0 μm of ol 2- benzyl indenes (component (B)) and 0.39mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen
The glass container in glove box under atmosphere is simultaneously dissolved in 30mL hexane.Then by MMAO (MMAO-3A, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in MMAO
The molar ratio of gadolinium be 100 to be added to glass container.Then 78.0 μm of ol diethyl aluminum chloride (component (E- are further added
1)), to generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 15.0 μm of ol gadoliniums
Agent composition is added to the 1L reactor including isoprene.The reaction system is maintained at 50 DEG C 90 minutes, and is carried out
The polymerization reaction of isoprene.
Then, the hexane solution 130g including 30g (0.56mol) 1,3-butadiene is added to polymer reaction solution.Again
It is secondary to maintain the reaction system at 50 DEG C 90 minutes, and carry out the polymerization reaction of 1,3-butadiene.
Then, polymerization reaction is terminated by adding 2mL isopropanol to reaction system.In addition, by being added to reactor
A large amount of methanol precipitate and separate reaction product.Then gains are dried in vacuo at 60 DEG C, (are produced to obtain polymer B A
Amount: 60g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment B2)
Other than in addition to the amount of diisobutyl aluminium hydride to be set as to 0.55mmol and using forming shown in table 2, with embodiment
The identical mode of B1 prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer B B (yield: 60g).
(embodiment B3)
Firstly, sufficiently dry stainless steel 1L will be added including the hexane solution 260g of the isoprene of 45g (0.66mol)
In reactor.
On the other hand, by 29.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 58.0 μm of ol 3- benzyl indenes (component (B)) and 0.39mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen
The glass container in glove box under atmosphere is simultaneously dissolved in 25mL hexane.Then by MMAO (MMAO-3A, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in MMAO
The molar ratio of gadolinium be 100 to be added to glass container.Then 58.0 μm of ol diethyl aluminum chloride (component (E- are further added
1)), to generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 22.5 μm of ol gadoliniums
Agent composition is added to the 1L reactor including isoprene.The reaction system is maintained at 50 DEG C 90 minutes, and is carried out
The polymerization reaction of isoprene.
Then, the hexane solution 65g including 15g (0.28mol) 1,3-butadiene is added to polymer reaction solution.Again
The reaction system is maintained at 50 DEG C 90 minutes, and carries out the polymerization reaction of 1,3-butadiene.
Then, polymerization reaction is terminated by adding 2mL isopropanol to reaction system.In addition, by being added to reactor
A large amount of methanol precipitate and separate reaction product.Then gains are dried in vacuo at 60 DEG C, (are produced to obtain polymer B C
Amount: 60g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment B4)
In addition to the ratio between isoprene and 1,3- butadiene are set as 80:20, use 1,3- butadiene as the first monomer and
Isoprene is as second comonomer and uses other than composition and condition shown in table 2, is prepared in a manner of identical with embodiment B1 poly-
It closes carbon monoxide-olefin polymeric and carries out polymerization reaction, to obtain polymer B D (yield: 60g).
(embodiment B5)
In addition to the ratio between isoprene and 1,3-butadiene are set as 88:12, using TMAO (TMAO341, by Tosoh
Finechem Corporation manufacture) it those of replaces MMAO, be set as polymeric reaction condition shown in table 2 and using 2 institute of table
Show other than composition and condition, polymerization catalyst composition is prepared in a manner of identical with embodiment B1 and carries out polymerization reaction, from
And obtain polymer B E (yield: 60g).
(embodiment B6)
Other than those of being set as polymeric reaction condition shown in table 2, prepared in a manner of identical with embodiment B5 poly-
It closes carbon monoxide-olefin polymeric and carries out polymerization reaction, to obtain polymer B F (yield: 60g).
(embodiment B7)
In addition to using 2- phenylindan to replace 3- benzyl indenes, using PMAO (TMAO-211, by Tosoh Finechem
Corporation manufacture) it replaces MMAO and uses other than composition and condition shown in table 2, the system in a manner of identical with embodiment B1
Standby polymerization catalyst composition simultaneously carries out polymerization reaction, to obtain polymer B G (yield: 60g).
(embodiment B8)
Other than using 3- methyl -2- phenylindan to replace 3- benzyl indenes, prepared in a manner of identical with embodiment B1 poly-
It closes carbon monoxide-olefin polymeric and carries out polymerization reaction, to obtain polymer B H (yield: 60g).
(embodiment B9)
Other than using indenes to replace 3- benzyl indenes, polymerization catalyst composition is prepared in a manner of identical with embodiment B1
And polymerization reaction is carried out, to obtain polymer B I (yield: 60g).
(comparative example B1)
In addition to using versatic acid neodymium (NEODYME VERSATATE 50, manufactured by Rhodia) to replace three (double-trimethyl first
Silicon alkylamides) gadolinium, without using 3- benzyl indenes, use PMAO (TMAO-211, by Tosoh Finechem Corporation system
Make) it replaces MMAO and uses other than composition and condition shown in table 2, polymerization catalyst is prepared in a manner of identical with embodiment B1
Composition simultaneously carries out polymerization reaction, to obtain polymer B J (yield: 60g).
(comparative example B2)
In addition to without using 3- benzyl indenes, using bis- (2- diphenylphosphinophenyl) amine (PNP ligand), do not use diethyl chlorine
Change aluminium and use other than composition and condition shown in table 2, polymerization catalyst composition is prepared in a manner of identical with embodiment B1 simultaneously
Polymerization reaction is carried out, to obtain polymer B K (yield: 60g).
(comparative example B3)
In addition to using bis- (2- phenyl indenyl) gadoliniums bis- (dimetylsilyl amides) to replace three (double-trimethyl silyls
Base amide) other than gadolinium, polymerization catalyst composition is prepared in a manner of identical with embodiment B1 and carries out polymerization reaction, but
To polymer.
(embodiment B10)
Other than in addition to using PMAO to replace MMAO and using forming shown in table 2 with condition, with side identical with embodiment B1
Formula prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer B M (yield: 60g).
(embodiment B11)
Other than without using diethyl aluminum chloride, polymerization catalyst composition is prepared in a manner of identical with embodiment B1
And polymerization reaction is carried out, to obtain polymer B N (yield: 60g).
(embodiment B12)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 19.5 μm of ol and using forming shown in table 2, with embodiment B1
Identical mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer B O (yield: 60g).
(embodiment B13)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 39.0 μm of ol and using forming shown in table 2, with embodiment B1
Identical mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer B P (yield: 60g).
(embodiment B14)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 390 μm of ol and using forming shown in table 2, with embodiment B1 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, but does not obtain polymer.
(embodiment B15)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 780 μm of ol and using forming shown in table 2, with embodiment B1 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, but does not obtain polymer.
The preparation of polymerization catalyst composition and isoprene-butadiene block copolymerization in each embodiment B and comparative example B
The details of the manufacture of object are listed in table 2.
It is calculate by the following formula the catalytic activity of polymerization catalyst composition during manufacturing.
(yield (kg))/((dosage (mol) of component (A)) × (reaction time (hour)))
(analysis of isoprene-butadiene block copolymer)
The analysis of (1) and (2) is carried out to the polymer B as above obtained.
(1) micro-structure (cis- -1,4- linkage content (%) of the part from isoprene and 3,4- vinyl bond content
Cis- -1,4- the linkage content (%) of (%), part from butadiene and vinyl bond content (%)) analysis
Polymer B each for gained is obtained using NMR (AVANCE 600, manufactured by Bruker)1H-NMR and13C-NMR
Spectrum.
For being originated from the part of isoprene, by passing through measurement1H-NMR and13Peak that C-NMR is obtained (1H-NMR: δ 4.6-
4.8 (3,4- vinyl units=CH2), 5.0-5.2 (Isosorbide-5-Nitrae-unit-CH=),13C-NMR: δ 23.4 (the cis- list of 1,4-
Member), 15.9 (Isosorbide-5-Nitraes-trans units), 18.6 (Unit 3,4-)) integral ratio, calculate cis--Isosorbide-5-Nitrae-linkage content (%) and 3,4-
Vinyl bond content (%).
For being originated from the part of butadiene, by passing through measurement1H-NMR and13Peak that C-NMR is obtained (1H-NMR: δ 4.8-5.0
(1,2- vinyl units=CH2), 5.2-5.4 (Isosorbide-5-Nitrae-unit-CH=),13C-NMR: δ 27.4 (Isosorbide-5-Nitrae-cis units),
32.7 (Isosorbide-5-Nitraes-trans units)) integral ratio, calculate cis--Isosorbide-5-Nitrae-linkage content (%) and vinyl bond content (%).
(2) analysis of number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn)
By gel permeation chromatography (GPC), (HLC-8220GPC is manufactured by Tosoh Corporation；Two columns:
TSKgel GMHXL, manufactured by Tosoh Corporation；Detector: differential refractometer (RI)), be with monodisperse polystyrene
Reference calculates number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) that polymer B is converted with polystyrene.Measuring temperature is
40 DEG C, eluting solvent THF.
The details of the analysis result of isoprene-butadiene block copolymer are listed in table 2 in each embodiment B and comparative example B.
Embodiment B1 to B15 and comparative example B1 shows the isoprene-butadiene using the disclosure to the comparison between B3
It is embedding can to manufacture isoprene-butadiene while reducing environmental pressure and manufacturing cost for the manufacturing method of block copolymer
Section copolymer.
Particularly, the comparison between embodiment B1 and comparative example B1 shows the manufacturing method using the disclosure, is reacted
The increase effect of the increase effect of the catalytic activity of system and cis- -1,4- linkage content.Between embodiment B1 and comparative example B2
Compare the manufacturing method shown using the disclosure, obtains the increase effect of the catalytic activity of reaction system.Embodiment B1 and compare
Comparison between example B3 shows the manufacturing method using the disclosure, and toxic and relatively expensive aromatic hydrocarbon is as the molten of polymerization reaction
Agent is not effect that is indispensable, and being reduced environmental pressure and manufacturing cost.
(manufacture of isoprene-butadiene random copolymer)
Isoprene-butadiene random copolymer is manufactured according to following experiments item.
(embodiment C1)
Firstly, will include the hexane solution 400g of 15g (0.22mol) isoprene and 45g (0.84mol) 1,3-butadiene
It is added in sufficiently dry stainless steel 1L reactor.
On the other hand, by 39.0 μm of ol tri- (double-trimethylsilylamide) gadolinium (Gd [N (SiMe3)2]3) (component
(A)), 78.0 μm of ol 2- benzyl indenes (component (B)), 0.45mmol diisobutyl aluminium hydride (component (C)) are added in nitrogen gas
The glass container in glove box under atmosphere is simultaneously dissolved in 30mL hexane.Then by MMAO (MMAO-3A, by Tosoh
Finechem Corporation manufacture) (component (D)) in the aluminium and three (double-trimethylsilylamide) gadoliniums in MMAO
The molar ratio of gadolinium be 100 to be added to glass container.Then 78.0 μm of ol diethyl aluminum chloride (component (E- are further added
1)), to generate polymerization catalyst composition.
Then, polymerization catalyst composition is taken out from glove box, and is urged polymerization with the amount comprising 30.0 μm of ol gadoliniums
Agent composition is added to the 1L reactor including isoprene and 1,3- butadiene.The reaction system is maintained 90 at 50 DEG C
Minute, and carry out the polymerization reaction (atactic polymerization reaction) of isoprene and 1,3-butadiene.
Then, polymerization reaction is terminated by adding 2mL isopropanol to reaction system.In addition, by being added to reactor
A large amount of methanol precipitate and separate reaction product.Then gains are dried in vacuo at 60 DEG C, (are produced to obtain polymer CA
Amount: 60g).
In entire manufacturing process, it is not used aromatic hydrocarbon (toluene etc.).
(embodiment C2)
Other than the ratio between isoprene monomer and 1,3-butadiene are set as 50:50, with side identical with embodiment C1
Formula prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CB (yield: 60g).
(embodiment C3)
Other than the ratio between isoprene monomer and 1,3-butadiene are set as 25:75, with side identical with embodiment C1
Formula prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CC (yield: 60g).
(embodiment C4)
In addition to using TMAO (TMAO341 is manufactured by Tosoh Finechem Corporation) to replace MMAO and using
Other than composition and condition shown in table 3, polymerization catalyst composition is prepared in a manner of identical with embodiment C2 and polymerize anti-
It answers, to obtain polymer CD (yield: 60g).
(embodiment C5)
In addition to use 2- phenylindan replace 3- benzyl indeno using composition shown in table 3 and condition other than, with embodiment C2
Identical mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CE (yield: 60g).
(embodiment C6)
In addition to use 3- methyl -2- phenylindan replace 3- benzyl indeno using composition shown in table 3 and condition other than, with reality
The identical mode of a C2 is applied to prepare polymerization catalyst composition and carry out polymerization reaction, thus obtain polymer CF (yield:
60g)。
(embodiment C7)
In addition to use 3- benzyl -2- phenylindan replace 3- benzyl indeno using composition shown in table 3 and condition other than, with reality
The identical mode of a C2 is applied to prepare polymerization catalyst composition and carry out polymerization reaction, thus obtain polymer CG (yield:
60g)。
(embodiment C8)
Other than using indenes that 3- benzyl indeno is replaced to use composition and condition shown in table 3, with identical with embodiment C2
Mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CH (yield: 60g).
(embodiment C9)
In addition to using versatic acid neodymium (NEODYME VERSATATE 50, manufactured by Rhodia) to replace three (double-trimethyl first
Silicon alkylamides) other than gadolinium, polymerization catalyst composition is prepared in a manner of identical with embodiment C2 and carries out polymerization reaction, from
And obtain polymer CI (yield: 60g).
(comparative example C1)
Other than without using 3- benzyl indenes, polymerization catalyst composition is prepared in a manner of identical with embodiment C2 and is gone forward side by side
Row polymerization reaction, to obtain polymer CJ (yield: 60g).
(comparative example C2)
In addition to using bis- (2- phenyl indenyl) gadoliniums bis- (dimetylsilyl amides) to replace three (double-trimethyl silyls
Base amide) gadolinium, without using 3- benzyl indeno using composition shown in table 3 and condition other than, the system in a manner of identical with embodiment C2
Standby polymerization catalyst composition simultaneously carries out polymerization reaction, but does not obtain polymer.
(embodiment C10)
In addition to using PMAO (TMAO-211 is manufactured by Tosoh Finechem Corporation) to replace MMAO and using
Other than composition and condition shown in table 3, polymerization catalyst composition is prepared in a manner of identical with embodiment C2 and polymerize anti-
It answers, to obtain polymer CL (yield: 60g).
(embodiment C11)
Other than without using diethyl aluminum chloride, polymerization catalyst composition is prepared in a manner of identical with embodiment C2
And polymerization reaction is carried out, to obtain polymer CM (yield: 60g).
(embodiment C12)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 19.5 μm of ol and using forming shown in table 3, with embodiment C2
Identical mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CN (yield: 60g).
(embodiment C13)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 39.0 μm of ol and using forming shown in table 3, with embodiment C2
Identical mode prepares polymerization catalyst composition and carries out polymerization reaction, to obtain polymer CO (yield: 60g).
(embodiment C14)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 390 μm of ol and using forming shown in table 3, with embodiment C2 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, but does not obtain polymer.
(embodiment C15)
Other than in addition to the amount of diethyl aluminum chloride to be set as to 780 μm of ol and using forming shown in table 3, with embodiment C2 phase
Same mode prepares polymerization catalyst composition and carries out polymerization reaction, but does not obtain polymer.
The preparation and isoprene-butadiene random copolymerization of polymerization catalyst composition in each embodiment C and comparative example C
The details of the manufacture of object are listed in table 3.
It is calculate by the following formula the catalytic activity of polymerization catalyst composition during manufacturing.
(yield (kg))/((dosage (mol) of component (A)) × (reaction time (hour)))
(analysis of isoprene-butadiene random copolymer)
The analysis of (1) and (2) is carried out to the polymer C as above obtained.
(1) micro-structure (cis- -1,4- linkage content (%) of the part from isoprene and 3,4- vinyl bond content
Cis- -1,4- the linkage content (%) of (%), part from butadiene and vinyl bond content (%)) analysis
Polymer C each for gained is obtained using NMR (AVANCE 600, manufactured by Bruker)1H-NMR and13C-NMR
Spectrum.
For being originated from the part of isoprene, by passing through measurement1H-NMR and13Peak that C-NMR is obtained (1H-NMR: δ 4.6-
4.8 (3,4- vinyl units=CH2), 5.0-5.2 (Isosorbide-5-Nitrae-unit-CH=),13C-NMR: δ 23.4 (the cis- list of 1,4-
Member), 15.9 (Isosorbide-5-Nitraes-trans units), 18.6 (Unit 3,4-)) integral ratio, calculate cis--Isosorbide-5-Nitrae-linkage content (%) and 3,4-
Vinyl bond content (%).
For being originated from the part of butadiene, by passing through measurement1H-NMR and13Peak that C-NMR is obtained (1H-NMR: δ 4.8-5.0
(1,2- vinyl units=CH2), 5.2-5.4 (Isosorbide-5-Nitrae-unit-CH=),13C-NMR: δ 27.4 (Isosorbide-5-Nitrae-cis units),
32.7 (Isosorbide-5-Nitraes-trans units)) integral ratio, calculate cis--Isosorbide-5-Nitrae-linkage content (%) and vinyl bond content (%).
(2) analysis of number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn)
By gel permeation chromatography (GPC), (HLC-8220GPC is manufactured by Tosoh Corporation；Two columns:
TSKgel GMHXL, manufactured by Tosoh Corporation；Detector: differential refractometer (RI)), be with monodisperse polystyrene
Reference calculates number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) that polymer C is converted with polystyrene.Measuring temperature is
40 DEG C, eluting solvent THF.
The details of the analysis result of isoprene-butadiene random copolymer are listed in table 3 in each embodiment C and comparative example C.
Embodiment C1 to C15 shows random using the isoprene-butadiene of the disclosure compared with comparative example C1 and C2
The manufacturing method of copolymer can manufacture isoprene-butadiene randomly altogether while reducing environmental pressure and manufacturing cost
Polymers.
Particularly, the comparison between embodiment C1 and comparative example C1 shows the manufacturing method using the disclosure, is reacted
The increase effect of the increase effect of the catalytic activity of system and cis- -1,4- linkage content.Between embodiment C1 and comparative example C2
Compare the manufacturing method shown using the disclosure, toxic and relatively expensive aromatic hydrocarbon is not absolute as the solvent of polymerization reaction
It is necessary, and the effect of environmental pressure and manufacturing cost can be reduced.
Industrial availability
According to the manufacturing method of the conjugated diolefin polymer of the disclosure, environmental pressure and manufacturing cost can be reduced.Furthermore
Using the conjugated diolefin polymer of the disclosure, it is capable of providing with high cis--Isosorbide-5-Nitrae-linkage content conjugated diolefin polymer.
In addition, the rubber composition of the disclosure can obtain the effect of the conjugated diolefin polymer of the disclosure.Furthermore the tire of the disclosure
The effect of the conjugated diolefin polymer of the disclosure can be obtained.
According to the manufacturing method of the conjugated diolefin polymer of the disclosure, particularly, isoprene-fourth can be suitably manufactured
Diene block copolymer and isoprene-butadiene random copolymer.
Claims (15)
1. a kind of manufacturing method of conjugated diolefin polymer, the method are characterized in that:
Using including rare-earth compound and with selected from by substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indenes
Come with the polymerization catalyst composition of the compound of at least one cyclopentadienyl skeleton of the group of substituted or unsubstituted fluorenes composition
Polymerized conjugated diene monomer,
Wherein the rare-earth compound is indicated by formula (1):
M-(AQ1)(AQ2)(AQ3) (1)
Wherein M indicates at least one element selected from the group being made of scandium, yttrium and lanthanide series；AQ1、AQ2And AQ3Respectively not
Same or identical functional group；A indicates nitrogen；And the rare-earth compound includes at least one M-A key.
2. the manufacturing method of conjugated diolefin polymer according to claim 1, wherein the polymerization catalyst composition is also
Including the organo-metallic compound indicated by formula (2):
YR1 aR2 bR3 c(2)
Wherein Y is the metallic element selected from the group being made of the 1st race of periodic table, the 2nd race, the 12nd race and the 13rd race；R1And R2Respectively
For hydrogen atom or the alkyl with 1 to 10 carbon atom；R3For the alkyl with 1 to 10 carbon atom；R1、R2And R3Phase each other
It is same or different；When Y is the metallic element of the 1st race, a is that 1 and b and c is 0；When the metallic element that Y is the 2nd race or the 12nd race
When, a and b is 1 and c is 0；When Y is the metallic element of the 13rd race, a, b and c are 1.
3. the manufacturing method of conjugated diolefin polymer according to claim 2, wherein in the formula (2), R1、R2And R3
At least one of be different.
4. the manufacturing method of conjugated diolefin polymer according to any one of claims 1 to 3, wherein having the ring penta 2
The compound of alkene skeleton is substituted or unsubstituted indenes.
5. the manufacturing method of conjugated diolefin polymer according to any one of claims 1 to 3, wherein the polymerization catalyst
Composition further includes aluminium alkoxide compound.
6. the manufacturing method of conjugated diolefin polymer according to claim 5, wherein the aluminium alkoxide compound is MMAO
Or TMAO.
7. the manufacturing method of conjugated diolefin polymer according to any one of claims 1 to 3, wherein the polymerization catalyst
Composition further includes halogen compounds.
8. the manufacturing method of conjugated diolefin polymer according to claim 7, wherein the halogen compounds with it is described dilute
The molar ratio of earth elements compound is 1.0 to 10.
9. the manufacturing method of conjugated diolefin polymer according to any one of claims 1 to 3, wherein the polymerization catalyst
Composition does not include aromatic hydrocarbon.
10. the manufacturing method of conjugated diolefin polymer according to any one of claims 1 to 3, wherein the conjugated diene
Monomer is isoprene and 1,3- butadiene.
11. a kind of conjugated diolefin polymer, by the system of the conjugated diolefin polymer described according to any of claims 1 to 10
Method manufacture is made,
Wherein cis- -1,4- linkage content is 95% or more.
12. a kind of isoprene-butadiene block copolymer, by conjugated diolefin polymer according to claim 10
Manufacturing method manufacture.
13. a kind of isoprene-butadiene random copolymer, by conjugated diolefin polymer according to claim 10
Manufacturing method manufacture.
14. a kind of rubber composition comprising conjugated diolefin polymer described in 1 to 13 any one according to claim 1.
15. a kind of tire is manufactured using rubber composition according to claim 14.
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| JP2014167727 | 2014-08-20 | ||
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| JP2014-167727 | 2014-08-20 | ||
| JP2014-167777 | 2014-08-20 | ||
| PCT/JP2015/003349 WO2016027402A1 (en) | 2014-08-20 | 2015-07-02 | Method for manufacturing conjugated diene polymer, conjugated diene polymer, rubber composition, and tire |
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| JP6598637B2 (en) * | 2015-10-29 | 2019-10-30 | 株式会社ブリヂストン | Method for producing polymerization catalyst composition, method for producing conjugated diene polymer, and method for producing modified conjugated diene polymer |
| JP6783246B2 (en) * | 2015-12-01 | 2020-11-11 | 株式会社ブリヂストン | Method for Producing Polymerization Catalyst Composition and Conjugated Diene Polymer |
| WO2017195634A1 (en) * | 2016-05-09 | 2017-11-16 | 株式会社ブリヂストン | Terminal-modified conjugated diene-based polymer, rubber composition, and rubber article |
| US20190161571A1 (en) * | 2016-05-24 | 2019-05-30 | Bridgestone Corporation | Terminal-modified conjugated diene polymer, rubber composition, rubber product and method for manufacturing terminal-modified conjugated diene polymer |
| RU2720010C1 (en) | 2016-11-09 | 2020-04-23 | Бриджстоун Корпорейшн | Block copolymers of polybutadiene and polyisoprene with high content of cis-1,4-bonds |
| US11472907B2 (en) | 2017-09-04 | 2022-10-18 | Bridgestone Corporation | Polymerization catalyst composition, polymer manufacturing method, polymer, rubber composition, and tire |
| CN111051369A (en) * | 2017-09-04 | 2020-04-21 | 株式会社普利司通 | Method for producing copolymer, rubber composition, and tire |
| IT201800005841A1 (en) * | 2018-05-30 | 2019-11-30 | PROCEDURE FOR THE PREPARATION OF RANDOM BUTADIENE-ISOPRENE COPOLYMERS WITH A HIGH CONTENT OF UNITS 1,4-CIS | |
| RU2684279C1 (en) * | 2018-06-26 | 2019-04-05 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") | Method of producing catalyst for copolymerisation of butadiene with isoprene |
| RU2684282C1 (en) * | 2018-06-26 | 2019-04-05 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") | Method of producing butadiene polymerisation catalyst |
| RU2684280C1 (en) * | 2018-06-26 | 2019-04-05 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") | Method for obtaining a catalyst for isoprene polymerization |
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|---|---|
| US10239964B2 (en) | 2019-03-26 |
| JPWO2016027402A1 (en) | 2017-06-08 |
| RU2658913C1 (en) | 2018-06-26 |
| CN106661140A (en) | 2017-05-10 |
| WO2016027402A1 (en) | 2016-02-25 |
| EP3184555B1 (en) | 2019-06-05 |
| EP3184555A1 (en) | 2017-06-28 |
| EP3184555A4 (en) | 2017-08-16 |
| JP6738734B2 (en) | 2020-08-12 |
| US20170233504A1 (en) | 2017-08-17 |
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